Quaternary ammonium salts of pyridine compounds



Patented Sept. 5, l950 QUATERNARY mmma comoum) Frederickdi mm. vmmgn. J.

Application August 5, 1947,

Serial No. 786,470 ,4 cum. (c1. soc-m) invention relates tonew chemicalcompounds which are derivatives of alkylene or polyalkylene polyaminesand which contain one: or

two quaternary .pyridinium radicals in the molecule. These compounds Ihave found to be .useful as bactericides and more particularly asbactericides having polyvalent metal sequestering action.

Quaternary pyridinium compounds are known to be useful bactericides. Theusefulness of these compounds is, however, somewhat limited in thepresence of hardwater flocks because the colloidal material tends tosurround and protect bacteria.

It is an object of this invention to prepare and.

provide the new chemical compounds of the kind referred to above, andgeneral formula:

' cur-000M; uicoou cmooou R-N,alkyl ene-( aikylcne)-NR whereinRiscontaining not more thanfour carbon atoms, and M is a member of thegroup consisting of alkali which have the metal and hydrogen. alkyl is along chain ali-' phatic group, and x is a member ofthe group consistingof chlorine, bromine, iodine and hy- In general the process of makingtheproducts herein described is a two-step process. The first steppreferably consists in reacting an, amino the compounds of thisinvention beillustrated in the examples-which follow.

. Example I,

Two molar equivalents of lauryi Ir-amino 'pyridinium chloride arecondensed with'one molar equivalent of di (chlor ethyl) amine by heatingthe two together. The hydrochloride salt which crystallizes outis'treated with caustic to set free .thebase. The intermediate productis believed v to have the following formula:

This product is reacted according to my U. 8. Patent 2,407,845 withformaldehyde, sodium cyanide and sodium hydroxide and then withhydrochloric acid, to yield a crystallizable compound believed to havethe formula:

ornooon omooon omooon rt-xormr-rt-(cnae-rt CuHn' v I \Ol Estimate If Twomolar equivalents of lauryl Y-amino pyridinium chloride are reactedaccording to .conventional procedure 1. e. by mixing and heatingtogether with one molar equivalentfof butylene 1,4 dichloride. Theproduct crystallizing out is the intermediate product as thehydrochloride. The free base is liberated with caustic. Therepyridinewith a suitable halogenated compound a suiting product-is then reactedas -in ExampleI to form an intermediate product, the intermediateproduct containing at least two amino nitrogen atoms. The second stepconsists in replacing thehydrogen atoms or the amino nitrogen atoms withacetic acid groups. The pyridyl group may or may not be treated beforethe first step with an alkyl halide to'form a quaternary salt.Preferably the I quarternary compound should be first-formed before thecondensation with the halogenated compound. The first step may becarried out by condensing amino pyridine with an aliphatic compound inwhich either one or both terminal carbon atoms are bonded to a halogenatom. The intermediate product may then be reacted according to my U. S.Patent 2,407,645. or to the chloracetic acid process, to replace withacetate groups the hydrogen atoms remaining on the amino nitrogen atoms.These processes. and modifications thereof, for making according tomyU.S. Patent"2,40l,645, and then with hydrochloric acid, .to yield a'crystallizable compound believed to have the formulas mm Ycncoonomooo'n' ,N- omn- I can! C! One molar equivalent of lauryl a-aminoW- 55 ridinium chloride is condensed with one molar equivalent ofl-chlor 2 amino ethane (ClCHaCHaNHz) Grant 01 by heating the twotogether. The resulting asaopoa product mono lauryl a-pyridyl ethylenediamine hydrochloride crystallizes out, is treated with NaOH to liberatethe free base, and is then reacted with sodium cyanide, formaldehyde andsodium hydroxide according to my U. 8. Patent 2,407,645. Finally theproduct is reacted with hydrochloric acid to yield a crystallizable com-I pound believed to have the formula:

omcoonornooom N zt-om-om-rt can. on

Ifdesired a halogen may be made to replace the --OH groups on thenitrogens by reacting with an acid such as H01, HBr, or HI. In such casethe sodium acetate groups become acetic acid groups.

Similarly other pyridines may be reacted with alkylene chlorides to formthe compounds of this invention.

Among the general characteristics of the compounds of this invention arethat they are excellent bactericides in general and particularly in thepresence of hard water and soap. The compounds disclosed above aregenerally yellowish colored crystalline salts which are soluble inwater, and in dilute alcohol solutions. They have an iso-electric pointof between 1.2 and 1.8. The compounds may be thought of as containingsolubilizing" groups (the acetate groups) and "non-solubilizing groups(the aryl groups). In those compounds containing multiple solubilizinggroups and only a single non-solubilizing" group the solubility in wateris quite marked. In those compounds containing a lower ratio of"solubilizing" to non-solubilizing" groups the solubility is decreased,although still appreciable. They are cationic active agents.

Good germicides are those having an aliphatic chain of 8 to 18 carbonatoms attached to the maximum bactericidal effect, such as the laurylderivatives shown above.

'to bacteria free serum.

Ifcopperinionicformisaddedtoanaqueous solution of one of the compoundsof this invention, a copper complex is apparently formed which issoluble in water. This complex has been found to be an excellentfungicide, and may be added .to hard water in the presence of soapwithout the 10 tion of a curdy precipitate.

The importan of the elimination of a hard water iiock in the presence ofastrong alkali or soap is great. It has been shown that upon theformation of a hard water flock, whether as the result of the formationof calcium hydroxide or calcium (or magnesium) soap, bacteria are pro- Amedium apparently bacteria-free after treatment with phenol, and havinga flock of calcium soap, was filtered, the precipitate was thoroughlywashed with sterile water and added The bacteria became active again.The compounds described herein eliminate any possibility flock.

- I claim:

1. A compound represented by the formula:

R-Nalkylene(Nalkylano).N-R

mcoou dmcoou dmooou wherein R is Gian.

N-CHr-CHr-N-ClIr-OKr-N nicoon mcoor'r cmooon 4. A compound representedby the formula cmcoom' dmooom N --OHr-CHs- CnHu omQon mnnnnxcx c.BERSWORTH.

No references cited.

of any contaminated

1. A COMPOUND REPRESENTED BY THE FORMULA: